Contribution to the study of PLA/sisal biocomposites behaviour under hydrothermal degrading conditions

A thorough understanding of the influence of the addition of natural fibers on the water absorption and solubility of bio-based composites is of importance in tailoring its performance in a wet environment. In this study, PLA/sisal biocomposites were prepared by compression moulding for different amounts of fiber. An accelerated hydrothermal degrading test was designed for several temperatures above the glass transition to analyse the behaviour of water absorption of PLA/sisal biocomposites. The diffusion coefficients and percentage of water at saturation for different hydrothermal conditions were characterized in terms of fiber content (10, 20 and 30%) and the use of maleic anhydride as a coupling agent. Microstructural changes occurred during and after the water absorption process were evaluated by thermal analysis and electron microscopy. Non-significant chemical changes were found in terms of back-bone chain scission. Surface analysis showed an important physical degradation promoted by the formation of microcracks around swollen fibers. This effect was more relevant the higher the fiber content was. As well, the use of maleic anhydride used as a coupling agent slightly promoted smaller cracks on PLA/sisal biocomposites

Long-term properties and end-of-life of polymers from renewable resources

The long-term properties and end-of-life of polymers are not antagonist issues. They actually are inherently linked by the duality between durability and degradation. The control of the service-todisposal pathway at useful performance, along with low-impact disposal represents an added-value. Therefore, the routes of design, production, and discarding of bio-based polymers must be carefully strategized. In this sense, the combination of proper valorisation techniques, i.e. material, energetic and/ or biological at the most appropriate stage should be targeted. Thus, the consideration of the end-of-life of a material for a specific application, instead of the end-of-life of a material should be the fundamental focus. This review covers the key aspects of lab-scale techniques to infer the potential of performance and valorisation of polymers from renewable resources as a key gear for sustainability

Suitability of Blends from Virgin and Reprocessed Polylactide: Performance and Energy Valorization Kinetics

A blending strategy of virgin and reprocessed polylactide may be postulated as an alternative to reduce the material cost at industrial level, and as a valorization route to plastic waste management of production scraps. The performance of blends prepared from virgin polylactide and polylactide mechanically reprocessed up to two cycles (PLA-V/R) was assessed in terms of thermo-oxidative stability, morphology, viscoelasticity and thermal kinetics for energetic valorization. PLA-V/R blends showed appropriate thermo-oxidative stability. The amorphous nature of polylactide was preserved after blending. The viscoelastic properties showed an increment of the mechanical blend effectiveness, which suggested the feasibility of using PLA-V/R blends under similar mechanical conditions to those of virgin PLA goods. Finally, it was shown that the energetic valorization of PLA-V/R blends would result in a more feasible process, due to the lower required activation energy, thus highlighting the advantages of the energetic demand for the process. In conclusion, PLA-V/R blends showed similar processability, service performance and valorization routes as virgin PLA and therefore could be relevant in the sustainable circular industry of bioplastics

Evaluation of gym users’ diet with muscle dysmorphia (bigorexia)

Objetivo: se muestra un estudio novedoso en el cual se ha analizado la dieta entre usuarios de gimnasio de la provincia de Alicante que padecen dismorfia muscular (DM). Metodología: se analizaron 141 gimnastas varones de varias salas de musculación de Alicante (zona urbana del sureste español) de edad entre 18-45 años, que persiguen el aumento de su masa muscular. Se tuvieron en cuenta el IMC (kg/m2) y la dieta realizada durante 24 horas. Y se ha determinado si padecían o no DM, a través de la Escala de satisfacción muscular. Resultados: la muestra está constituida por 141 varones, de los cuales 45 padecen DM y 96 no, según la Escala de satisfacción muscular. Se calculó el consumo de proteínas, siendo superior a 1,5 g/kg/día en el grupo sin DM y superior a 2 g/kg/día en el grupo con DM. Al analizar los demás macronutrientes los resultados indican que la proporción de hidratos de carbono, grasas y sus porcentajes según grado de insaturación están dentro de las recomendaciones, excepto el colesterol, que las supera, y la cantidad de fibra, que es ligeramente inferior. En relación a los micronutrientes en todos los casos están dentro de las recomendaciones excepto en el caso del yodo, que en los DM es ligeramente inferior. Conclusión: los individuos con DM realizan una dieta normocalórica y adecuada en hidratos de carbono y lípidos; sin embargo, los valores de proteína ingerida exceden los límites propuestos según la evidencia científica para el desarrollo de masa muscular en los deportes de fuerza.Objective: it is an innovative study where has been analyzed the diet among gym users with Muscle Dysmorphia (MD) of gyms in the province of Alicante. Methodology: it have been analyzed 141 male gymnasts of several gyms of Alicante (urban area of southeastern Spanish) aged between 18-45 years old, who purpose increasing their muscle mass. Were considered BMI (kg/m2) and 24 hour diet. And it has been determined whether or not suffer MD trough Muscle Appearance Satisfaction Scale. Results: the sample consisted of 141 men, of whom 45 are MD and 96 are not according to Muscle Appearance Satisfaction. Protein intake was calculated and was greater than 1.5 g/kg/day in patients without MD and greater than 2 g/kg/day in the MD group. Analyzing the other nutrients, results show that the proportion of carbohydrates and fats and their percentages by degree of instauration are within the recommendations except cholesterol which exceeds and the amount of dietary fiber that is slightly lower. In relation to micronutrients are within the recommendations in all cases except iodine which is slightly lower in MD. Conclusion: individuals with MD do a balanced energy and adequate carbohydrate and fat diet, however protein intake values exceed the limits proposed according to the scientific evidence for muscle mass development in strength sports

Performance of polyester-based electrospun scaffolds under in vitro hydrolytic conditions: From short-term to long-term applications

The evaluation of the performance of polyesters under in vitro physiologic conditions is essential to design scaffolds with an adequate lifespan for a given application. In this line, the degradation-durability patterns of poly(lactide-co-glycolide) (PLGA), polydioxanone (PDO), polycaprolactone (PCL) and polyhydroxybutyrate (PHB) scaffolds were monitored and compared giving, as a result, a basis for the specific design of scaffolds from short-term to long-term applications. For this purpose, they were immersed in ultra-pure water and phosphate buffer solution (PBS) at 37 °C. The scaffolds for short-time applications were PLGA and PDO, in which the molar mass diminished down to 20% in a 20-30 days lifespan. While PDO developed crystallinity that prevented the geometry of the fibres, those of PLGA coalesced and collapsed. The scaffolds for long-term applications were PCL and PHB, in which the molar mass followed a progressive decrease, reaching values of 10% for PCL and almost 50% for PHB after 650 days of immersion. This resistant pattern was mainly ascribed to the stability of the crystalline domains of the fibres, in which the diameters remained almost unaffected. From the perspective of an adequate balance between the durability and degradation, this study may serve technologists as a reference point to design polyester-based scaffolds for biomedical applications

Influence of the Molecular Weight on PVA/GO Composite Membranes for Fuel Cell Applications

Composite polymer electrolyte membranes were prepared with poly (vinyl alcohol) (PVA). Two different molecular weight (Mw), 67·103 and 130·103 g·mol−1 were selected, cross-linked with sulfosuccinic acid (SSA) and doped graphene oxide (GO). The effects on the membranes obtained from these polymers were characterized in order to evaluate the fuel cell performance. Electron microscopy showed a proper nanoparticle distribution in the polymer matrix. The chemical structure was evaluated by Fourier transform infrared spectroscopy. The absence of a crystalline structure and the enhancement on the thermal stability with the addition of 1% of GO was demonstrated by thermal characterization. Total transference number and protonic conductivity were correlated to the performance of a hydrogen fuel cell. Overall, a power increase in the composite membranes with lower molecular weight was observed. Shorter polymer chains may improve protonic conductivity and consequently the fuel cell performance

In vitro validation of biomedical polyester-based scaffolds: Poly(lactide-co-glycolide) as model-case

Monitoring and understanding the in vitro behaviour of polyester based scaffolds both comprising the study of the hydrolytic degradation and the cell seeding viability is essential to ensure the desired functionality, according to a given biomedical purpose. As a model case to compare the performance of techniques to monitor the in vitro behaviour, poly(lactide-co-glycolide) (PLGA) scaffolds were chosen. The in vitro hydrolytic degradation of PLGA scaffolds was carried out in water and phosphate buffered saline (PBS). The evolution of the mass loss, the molar mass, the thermal properties and the surface morphology were monitored. The hydrolytic degradation media was correspondingly evaluated by means of the study of the pH, the amount of acid released and the conductivity. In addition, the in vitro biocompatibility regarding the cell culture viability was studied under physiological conditions. The cellular adhesion, cellular ability to proliferate on the scaffold, the scaffold inflammatory profile and the effect of the scaffold degradation compounds on the cells were assessed. A comparative analysis of the exploited techniques in terms of promptness of identification, depth of knowledge, simplicity of obtaining results and cost of the technique was implemented. The results showed that, depending on the balance between the interest in ascertaining the trigger of degradation or deep into the knowledge of the causes and effects of cell culture viability, an appropriate plan of analysis of the validation of polyester-based scaffolds could be designed.Peer ReviewedPostprint (author's final draft

Effect of the dissolution time into an acid hydrolytic solvent to taylor electrospun nanofibrous polycaprolactone scaffolds

The hydrolysis of the polycaprolactone (PCL) as a function of the dissolution time in a formic/ acetic acid mixture was considered as a method for tailoring the morphology of nanofibrous PCL scaffolds. Hence, the aim of this research was to establish a correlation between the dissolution time of the polymer in the acid solvent with the physicochemical properties of the electrospun nanofibrous scaffolds and their further service life behaviour. The physico-chemical properties of the scaffolds were assessed in terms of fibre morphology, molar mass and thermal behaviour. A reduction of the molar mass and the lamellar thickness as well as an increase of the crystallinity degree were observed as a function of dissolution time. Bead-free fibres were found after 24 and 48 h of dissolution time, with similar diameter distributions. The decrease of the fibre diameter distributions along with the apparition of beads was especially significant for scaffolds prepared after 72 h and 120 h of dissolution time in the acid mixture. The service life of the obtained devices was evaluated by means of in vitro validation under abiotic physiological conditions. All the scaffolds maintained the nanofibrous structure after 100 days of immersion in water and PBS. The molar mass was barely affected and the crystallinity degree and the lamellar thickness increased along immersion, preventing scaffolds from degradation. Scaffolds prepared after 24 h and 48 h kept their fibre diameters, whereas those prepared after 72 h and 120 h showed a significant reduction. This PCL tailoring procedure to obtain scaffolds that maintain the nanoscaled structure after such long in vitro evaluation will bring new opportunities in the design of longterm biomedical patches

Degradation of Plasticised Poly(lactide) Composites with Nanofibrillated Cellulose in Different Hydrothermal Environments

In this study, bionanocomposite films based on poly(lactide) (PLA) plasticised with poly(ethylene glycol) (PEG) (7.5 wt%) and reinforced with various contents of nanofibrillated cellulose (NFC) (1, 3, 5 wt%) were prepared. The hydrothermal degradation was investigated through immersion in several aqueous environments at temperatures of 8, 23, 58, and 70 °C as a function of time (7, 15, 30, 60, 90 days). The effect of water immersion on the physicochemical properties of the materials was assessed by monitoring the changes in the morphology, thermo-oxidative stability, thermal properties, and molar mass through field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). The hydrothermal degradation behaviour was not critically affected regardless of the nanofibrillated cellulose content. All the materials revealed certain integrity towards water immersion and hydrolysis effects at low temperatures (8 and 23 °C). The low hydrothermal degradation may be an advantage for using these PLA biocomposites in contact with water at ambient temperatures and limited exposure times. On the other hand, immersion in water at higher temperatures above the glass transition (58 and 70 °C), leads to a drastic deterioration of the properties of these PLA-based materials, in particular to the reduction of the molar mass and the disintegration into small pieces. This hydrothermal degradation behaviour can be considered a feasible option for the waste management of PLA/PEG/NFC bionanocomposites by deposition in hot aqueous environments

Functionalised Poly(Vinyl Alcohol)/Graphene Oxide as Polymer Composite Electrolyte Membranes

[EN] Crosslinked poly(vinyl alcohol) (PVA) based composite films were prepared as polyelectrolyte membranes for low temperature direct ethanol fuel cells (DEFC). The membranes were functionalised by means of the addition of graphene oxide (GO) and sulfonated graphene oxide (SGO) and crosslinked with sulfosuccinic acid (SSA). The chemical structure was corroborated and suitable thermal properties were found. Although the addition of GO and SGO slightly decreased the proton conductivity of the membranes, a significant reduction of the ethanol solution swelling and crossover was encountered, more relevant for those functionalised with SGO. In general, the composite membranes were stable under simulated service conditions. The addition of GO and SGO particles permitted to buffer the loss and almost retain similar proton conductivity than prior to immersion. These membranes are alternative polyelectrolytes, which overcome current concerns of actual commercial membranes such as the high cost or the crossover phenomenon.The authors would like to thank the support of the European Union through the European Regional Development Funds (ERDF). The Spanish Ministry of Economy, Industry and Competitiveness, is thanked for the research project POLYDECARBOCELL (ENE2017-86711-C3-1-R). The Spanish Ministry of Education, Culture and Sports is thanked for the FPU grant for O. Gil-Castell (FPU13/01916).Gil Castell, Ó.; Cerveró, R.; Teruel Juanes, R.; Badia, JD.; Ribes Greus, MD. (2019). Functionalised Poly(Vinyl Alcohol)/Graphene Oxide as Polymer Composite Electrolyte Membranes. Journal of Renewable Materials. 7(7):655-665. https://doi.org/10.32604/jrm.2019.04401S6556657